selective nickel based hydrogenation catalyst and the preparation thereof

ABSTRACT

A selective nickel-based hydrogenation catalyst with alumina as carrier and the preparation thereof, characterized in that: provided that the catalyst is weighed 100%, it comprises nickel oxide 14-20% as active component, lanthanum oxide and/or cerium oxide 1-8%, VIB element oxide 1-8% as aids, 2-8% silica, 1-8% alkaline earth metal oxides. The catalyst specific surface area is 60-150 m 2 /g, and the pore volume is 0.4-0.6 ml/g. The catalyst has good hydrogenation performance, especially impurity and colloid resistance and hydrogenation stability. The catalyst can be applied to the diolefin selective hydrogenation of medium or low-distillate oil, especially of the full-distillates pyrolysis gasoline.

FIELD OF THE INVENTION

The present invention relates to a selective nickel-based hydrogenationcatalyst and the preparation thereof. The catalyst is useful inselective hydrogenation of medium or low distillate oil, in particular,in the first-stage selective hydrogenation process of pyrolysis gasolinedistillate.

BACKGROUND OF THE INVENTION

Pyrolysis gasoline is the by-product of steam cracking to make ethylene,which approximately comprises more than 50% of the production capacityof ethylene. Pyrolysis gasoline contains highly unsaturatedhydrocarbons, such as diolefin, styrene and the like, which can beconverted into corresponding monoolefin by selective hydrogenation. Withthe increasing ethylene production capability in China, thehydrogenation of pyrolysis gasoline has developed toward thehydrogenation of full distillate using nickel-based catalyst. Due to thevariability of the pyrolysis gasoline raw materials and the differencesin pyrolysis apparatus and pyrolysis modes, the pyrolysis gasoline rawmaterials are deteriorated, and the hydrogenation load and the contentof impurity such as arsenic are increased, thereby causing the inferiorperformance of palladium-based catalyst for first-stage hydrogenation.For noble metal catalyst, its arsenic and colloid resistance as well aswater resistance is low, since the impurity arsenic tends to occupy theempty orbital of Pd, and Pd is located on the surface layer of thecatalyst with a content of only parts per thousand. For non-noble metalcatalyst, it has certain arsenic tolerance and colloid and waterresistance due to the structural difference and high metal content;moreover, it has relatively remarkable price advantage. Thus, there isneed of the market and technical competition to develop a newnickel-based catalyst for first-stage hydrogenation of full distillatepyrolysis gasoline.

U.S. Pat. No. 3,472,763 reports a Ni/Al₂O₃ catalyst for the selectivehydrogenation of diolefin, comprising 1-20% nickel as active component,1-5% MoO₃ as aids, 1-5% alkali metal and alkaline earth metal as aids,and having a pore volume of more than 0.4 ml/g and a specific surfacearea of more than 30 m²/g. This catalyst is prepared by impregnating theAl₂O₃ carrier with the aqueous solution of above-mentioned activecomponent and aids. CN1218822A reports a Ni/Al₂O₃ catalyst suitable forthe selective hydrogenation of pyrolysis gasoline distillates. Thiscatalyst is prepared by loading nickel on alumina carrier comprisinglithium or alkaline earth metal. However, this catalyst is not good atwithstanding the hydrogenation load and its hydrogenation stability isto be improved.

An excellent selective hydrogenation catalyst should have higherhydrogenation activity and better selectivity. More importantly, itshould have good stability. That is to say, it is necessary for suchcatalyst to have capability to resist impurity and colloid, therebyprolonging its lifetime.

SUMMARY OF THE INVENTION

The aim of the present invention is to develop a nickel-based Al₂O₃supported catalyst for selective hydrogenation of diolefin. The catalysthas good hydrogenation performance, especially has good hydrogenationstability, and can be applied to the selective hydrogenation of fulldistillate pyrolysis gasoline.

The selective nickel-based hydrogenation catalyst of the presentinvention, with alumina as carrier, is characterized in that based onthe total weight of the catalyst, it comprises:

14-20% nickel oxide as active component;

1-8% lanthanum oxide and/or cerium oxide;

1-8% VIB group element oxide as aids;

2-8% silica;

1-8% alkaline earth metal oxide;

wherein said catalyst has a specific surface area of 60-150 m²/g and apore volume of 0.4-0.6 ml/g. This catalyst is especially useful in thediolefin selective hydrogenation of medium or low distillate oil, inparticular, in the diolefin selective hydrogenation of full distillatepyrolysis gasoline.

The present invention also provides a method for preparing suchcatalyst, comprising:

adding silica or its precursor and alkaline earth metal oxide or itsprecursor into alumina carrier;

calcinating at the temperature of 800-1100° C. for 3-6 hours to form themodified alumina carrier;

adding the soluble salts of nickel, lanthanum and/or cerium and VIBgroup element into water;

after fully dissolution, adjusting the pH of the solution to 4-5 to forman impregnating solution;

impregnating the modified alumina carrier with the impregnatingsolution;

drying at the temperature of 40-120° C.; and

calcinating at the temperature of 350-450° C. for 3-6 hours, therebyobtaining the resultant catalyst.

In particular, the present invention preferably recommends that themodified alumina carrier is prepared by:

adding silica sol, nitric acid and water into alumina hydrate(pseudo-boehmite);

after kneading and extruding, drying at the temperature of 40-120° C.;

calcinating at the temperature of 300-600° C. for 4-6 hours;

impregnating the formed carrier with the impregnating solution formed byadding alkaline earth metal oxide into water;

drying at the temperature of 40-120° C.; and

calcinating at the temperature of 800-1100° C. for 4-6 hours, therebyforming the modified alumina carrier with desired physical properties.

The catalyst according to the present invention comprises 2-8% silica,which may increase the stability of the catalyst, especially the carrierduring calcination. Preferably, the content of silica is 3-4%.Preferably, the content of nickel oxide is 15-19%.

The catalyst according to the present invention comprises alkaline earthmetal, which may adjust the acidity of the catalyst after calcinationand improve the colloid resistance during hydrogenation reaction.Preferably, the alkaline earth metal is magnesium and/or strontium. Thecontent of alkaline earth metal oxide is preferably 2-5%.

The lanthanum and/or cerium are added in the form of nitrate dissolvedin the impregnating solution so as to improve the hydrogenation activityand stability of the catalyst. Preferably, the content of lanthanumoxide and/or cerium oxide is 3-5%.

The VIB group element is added to improve the hydrogenation activity andimpurity (for example, sulfur) resistance of the catalyst. Preferably,the VIB group element is one or more of Cr, Mo and W. The content of VIBgroup element oxide is preferably 3-6%.

The solution of the active component and aids are impregnated onto theresultant catalyst carrier in twice to increase the dispersity of theactive component of the catalyst and improve the activity and stabilityof catalyst.

The compounds of nickel (as active component), magnesium, strontiumlanthanum and cerium (as aids) in above-mentioned preparation processmay be in the form of sulfate, nitrate and halide and so on. Preferably,they are in the form of nitrate, since nitrate is easily soluble inwater to be fully dissolved and form stable solution.

The alumina hydrate, as the starting material for preparing the catalystaccording to the present invention, may be alumina hydrates prepared bycarbon dioxide method, ammonia method, and nitric acid method and so on.The alumina hydrate prepared by nitric acid method is preferable due toits better hydrogenation performance.

The catalyst according to the present invention should be reduced underhydrogen at the temperature of 350-400° C. for 5-6 hours prior to use.During the reduction, the volume ratio of hydrogen to catalyst is 150:1to 500:1.

DETAILED DESCRIPTION OF THE INVENTION Source of Starting Materials

Nickel nitrate: available from Xi′ an Chemical Reagent Factory;

Magnesium nitrate and strontium nitrate: available from Shanghai ColloidChemical Plant;

Cerium nitrate and lanthanum nitrate: available from Shensheng ReagentFactory, Fufeng, Yixing, Jiangsu;

Alumina powder: available from Lanhua Xiangxin Additives Factory.

Example 1

140 ml water, 5 ml nitric acid (the content of which is 60%) and 16 mlsilica sol (comprising 40% silica) are added to 300 g pseudo-boehmitealumina powder. After kneading and extruding, the formed alumina carrieris dried in air at 120° C., and then calcinated at 560° C. for 4 hours.100 g calcinated carrier is impregnated with a solution form bydissolving 26 g magnesium nitrate into water, dried in air at 120° C.,and calcinated at 1050° C. for 4 hours, thereby obtaining the modifiedAl₂O₃ carrier.

10 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 2.1 g cerium nitrate and 0.3 g ammonium molybdate are added.The pH of the solution is adjusted to 4. Then 10 g carrier isimpregnated with the solution, aged for 12 hours, dried at 120° C., andcalcinated at 400° C. for 4 hours, thereby obtaining the catalyst.

Comparative Example 1

140 ml water and 5 ml nitric acid (the content of which is 60%) areadded to 300 g pseudo-boehmite alumina powder. After kneading andextruding, the formed alumina carrier is dried in air at 120° C., andthen calcinated at 560° C. for 4 hours. 100 g calcinated carrier isimpregnated with a solution formed by dissolving 16.7 g magnesiumnitrate and 3 g strontium nitrate into water, dried in air at 120° C.,and calcinated at 1050° C. for 4 hours, thereby obtaining the Al₂O₃carrier.

10 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 2.1 g cerium nitrate and 0.3 g ammonium molybdate are added.The pH of the solution is adjusted to 4. Then 10 g carrier isimpregnated with the solution, aged for 12 hours, dried at 120° C., andcalcinated at 400° C. for 4 hours, thereby obtaining the catalyst.

Example 2

140 ml water, 5 ml nitric acid (the content of which is 60%) and 14 mlsilica sol (comprising 40% silica) are added to 300 g pseudo-boehmitealumina powder. After kneading and extruding, the formed alumina carrieris dried in air at 120° C., and then calcinated at 460° C. for 4 hours.100 g calcinated carrier is impregnated with a solution formed bydissolving 20 g magnesium nitrate and 3.5 g strontium nitrate intowater, dried in air at 120° C., and calcinated at 1000° C. for 4 hours,thereby obtaining the Al₂O₃ carrier.

8.6 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 1.5 g lanthanum nitrate and 0.6 g ammonium tungstate areadded. The pH of the solution is adjusted to 4. Then 10 g carrier isimpregnated with the solution, aged for 12 hours, dried at 120° C., andcalcinated at 350° C. for 4 hours, thereby obtaining the catalyst.

Comparative Example 2

140 ml water, 5 ml nitric acid (the content of which is 60%) and 14 mlsilica sol (comprising 40% silica) are added to 300 g pseudo-boehmitealumina powder. After kneading and extruding, the formed alumina carrieris dried in air at 120° C., and calcinated at 1000° C. for 4 hours,thereby obtaining the Al₂O₃ carrier.

8.6 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 1.5 g lanthanum nitrate and 0.6 g ammonium tungstate areadded. The pH of the solution is adjusted to 4. Then 10 g carrier isimpregnated with the solution, aged for 12 hours, dried at 120° C., andcalcinated at 350° C. for 4 hours, thereby obtaining the catalyst.

Example 3

140 ml water, 5 ml nitric acid (the content of which is 60%) and 9 mlsilica sol (comprising 40% silica) are added to 300 g pseudo-boehmitealumina powder. After kneading and extruding, the formed alumina carrieris dried in air at 120° C., and then calcinated at 460° C. for 4 hours.100 g calcinated carrier is impregnated with a solution formed bydissolving 15.5 g magnesium nitrate into water, dried in air at 120° C.,and calcinated at 1030° C. for 4 hours, thereby obtaining the Al₂O₃carrier.

7.9 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 0.63 g cerium nitrate, 0.62 g lanthanum nitrate and 0.5 gammonium tungstate are added. The pH of the solution is adjusted to 4.Then 10 g carrier is impregnated with the solution, aged for 12 hours,dried at 120° C., and calcinated at 400° C. for 4 hours, therebyobtaining the catalyst.

Comparative Example 3

140 ml water is added to 300 g pseudo-boehmite alumina powder. Afterkneading and extruding, the formed alumina carrier is dried in air at120° C., and calcinated at 1030° C. for 4 hours, thereby obtaining theAl₂O₃ carrier.

7.9 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 0.6 g ammonium molybdate is added. The pH of the solution isadjusted to 4. Then 10 g carrier is impregnated with the solution, agedfor 12 hours, dried at 120° C., and calcinated at 400° C. for 4 hours,thereby obtaining the catalyst.

Example 4

140 ml water, 5 ml nitric acid (the content of which is 60%) and 12 mlsilica sol (comprising 40% silica) are added to 300 g pseudo-boehmitealumina powder. After kneading and extruding, the formed alumina carrieris dried in air at 120° C., and then calcinated at 460° C. for 4 hours.100 g calcinated carrier is impregnated with a solution formed bydissolving 5.8 g strontium nitrate into water, dried in air at 120° C.,and calcinated at 1020° C. for 4 hours, thereby obtaining the Al₂O₃carrier.

9.5 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 1.1 g cerium nitrate, 1.1 g lanthanum nitrate and 0.6 gpotassium chromate are added. The pH of the solution is adjusted to 4.Then 10 g carrier is impregnated with the solution, aged for 12 hours,dried at 120° C., and calcinated at 350° C. for 4 hours, therebyobtaining the catalyst.

Comparative Example 4

140 ml water, 5 ml nitric acid (the content of which is 60%) and 12 mlsilica sol (comprising 40% silica) are added to 300 g pseudo-boehmitealumina powder. After kneading and extruding, the formed alumina carrieris dried in air at 120° C., and then calcinated at 460° C. for 4 hours.100 g calcinated carrier is impregnated with a solution formed bydissolving 21.6 g magnesium nitrate into wate, dried in air at 120° C.,and calcinated at 1020° C. for 4 hours, thereby obtaining the Al₂O₃carrier.

9.5 g nickel nitrate is added to 20 ml water with stirring. Whilestirring, 1.1 g cerium nitrate is added. The pH of the solution isadjusted to 4. Then 10 g carrier is impregnated with the solution, agedfor 12 hours, dried at 120° C., and calcinated at 350° C. for 4 hours,thereby obtaining the catalyst.

INDUSTRIAL APPLICABILITY Analysis Method

Distillation range of oil products: measured according to PetroleumProduct Testing Method SYB-2110-60;

Iodine value: measured according to IC1 method, expressed in g I₂/100 goil;

Diolefin: measured according to maleic anhydride method, expressed in gI₂/100 g oil;

Arsenic content: measured by DV-4300 atomic emission spectroscopy;

Sulfur content: measured by WK-2B microcoulometric detector;

Colloid: measured according to Petroleum Product Testing MethodSYB-2103-60.

The full distillate pyrolysis gasoline is used as the startingmaterials, the properties of which are shown in Table 1. The catalystsof Examples 1, 2, 3 and 4 as well as Comparative Examples 1, 2, 3 and 4are evaluated on 100 ml adiabatic bed hydrogenation apparatus. Firstly,the catalyst is reduced under hydrogen at the temperature of 350-400° C.for 10 hours. The temperature is lowered to 60° C. After the catalyst isinactivated by cyclohexane containing 1000 ppm dimethyl disulfide for 2hours, the raw oil is added.

Reaction Condition:

Reaction pressure: 2.8 MPa,

Intake temperature: room temperature ˜60° C.,

Air speed of fresh raw oil: 3.5h⁻¹,

The volume ratio of hydrogen to oil: 200:1 (based on the fresh oil).

The evaluation is carried out for 200 hours. And the iodine value anddiolefin of the products are analyzed every 6 hours. The average data ofthe iodine value and diolefin of the product for each catalyst duringthe 200-hour evaluation are shown in Table 2.

TABLE 1 Indexes of hydrogenation raw oil (C₅-C₉) Sulfur Arsenic Iodinevalue × Diolefin × Distillation content Colloid × Density content Color10⁻² (g/g) 10⁻² (g/g) range (° C.) (ppm) 10⁻² (mg/ml) (g/ml) (ppb)Yellow 89.2 38.5 45-205 96 6.0 0.815 <20

TABLE 2 Catalyst composition and average data of 200-hour evaluation inevery example and comparative example Catalyst Example ComparativeExample Comparative Example Comparative Example Comparative Index 1Example 1 2 Example 2 3 Example 3 4 example 4 Product diolefin × 10⁻²(g/g) 1.0 1.18 0.8 1.82 0.9 1.18 0.95 1.15 Product iodine value × 10⁻²(g/g) 41.3 44.2 39.8 45.3 40.2 42.6 40.5 41.8 The colloid content after6.1 5.9 5.8 7.5 6.2 8.6 6.5 6.8 200 hours reaction % Specific surfacearea of 93.78 88.02 105.3 108.9 88.26 87.29 95.84 104.93 the catalyst/m²· g⁻¹ Specific pore volume of 0.42 0.48 0.46 0.43 0.52 0.45 0.44 0.46the catalyst/cm³ · g⁻¹ Active Nickel 18.8 18.8 16.6 16.6 15.6 16.1 17.918.9 component oxide and Silica 4.3 / 3.7 3.7 2.4 / 3.2 3.2 aidsLanthanum / / 4.2 4.2 1.8 / 3.0 / content/ oxide wt % Cerium 6.1 6.1 / /1.9 / 3.2 3.4 oxide Magnesium 3.9 2.4 2.9 / 2.4 / / 3.3 oxide Strontium/ 1.6 1.8 / / / 3.2 / oxide Molybdenum 1.7 1.7 / / / 3.9 / / oxideTungsten / / 3.8 3.8 3.3 / / / oxide Chromium / / / / / / 2.3 / oxide

1000-hour long period evaluation is performed on the catalyst of Example2. The evaluation was carried out on 100 ml adiabatic bed hydrogenationapparatus. Firstly, the catalyst is reduced under hydrogen at thetemperature of 400-450° C. for 10 hours. The temperature is lowered to60° C. After the catalyst is inactivated by cyclohexane containing 1000ppm dimethyl disulfide for 3 hours, the raw oil is added.

Reaction Condition:

Reaction pressure: 2.8 MPa,

Intake temperature: room temperature ˜70° C.,

Air speed of fresh raw oil: 2.8h⁻¹,

The volume ratio of hydrogen to oil: 200:1 (based on the fresh oil).

The iodine value and diolefin of the product are analyzed every 12hours. The average data during every 200 hours are taken. The indexes ofhydrogenation raw oil (C₅-C₉) are shown in Table 3.

TABLE 3 Indexes of hydrogenation raw oil (C₅-C₉) Sulfur Arsenic Iodinevalue × Diolefin × Distillation content Colloid × Density content Color10⁻² (g/g) 10⁻² (g/g) range (° C.) (ppm) 10⁻² (mg/ml) (g/ml) (ppb)Yellow 88.5 39.5 45-205 86 7 0.815 26

The results of evaluation are shown in Table 4. During the 1000-houroperation, the iodine value and diolefin value of the hydrogenationproduct remain at low level, which sufficiently indicates that thecatalyst in Example 2 has good stability and hydrogenation activity.

TABLE 4 1000-hour evaluation data for catalysts of Example 2 andComparative Example 3 Hydrogenation product index Catalyst ofComparative Cumulative Catalyst of Example 2 Example 3 operationDiolefin × Iodine value × Diolefin × Iodine value × time (h) 10⁻² (g/g)10⁻² (g/g) 10⁻² (g/g) 10⁻² (g/g) 200 0.8 36.8 0.8 36.0 400 0.8 37.2 1.138.9 600 1.0 38.6 1.4 39.8 800 1.2 39.6 1.8 40.3 1000 1.4 40.2 2.5 43.6

In summary, the hydrogenation catalyst according to the presentinvention has good hydrogenation performance, especially has impurityand colloid resistance as well as good hydrogenation stability. Thecatalyst can be applied to selective hydrogenation of diolefinunsaturated hydrocarbons, especially the first-stage selectivehydrogenation process of full distillate pyrolysis gasoline.

1. A selective nickel-based hydrogenation catalyst comprising alumina asa carrier, characterized in that based on the total weight of thecatalyst, the catalyst comprises: 14-20% nickel oxide as an activecomponent; 1-8% lanthanum oxide and/or cerium oxide; 1-8% VIB groupelement oxide as aids; 2-8% silica; and 1-8% alkaline earth metal oxide;wherein said catalyst has a specific surface area of 60-150 m²/g and apore volume of 0.4-0.6 ml/g.
 2. The selective nickel-based hydrogenationcatalyst according to claim 1, characterized in that the nickel oxide inthe catalyst is in the amount of 15-19%.
 3. The selective nickel-basedhydrogenation catalyst according to claim 1, characterized in that thelanthanum oxide and/or cerium oxide in the catalyst is in the amount of3-5%.
 4. The selective nickel-based hydrogenation catalyst according toclaim 1, characterized in that said alkaline earth metal is magnesiumand/or strontium.
 5. The selective nickel-based hydrogenation catalystaccording to claim 1, characterized in that the alkaline earth metaloxide in the catalyst is in the amount of 2-5%.
 6. The selectivenickel-based hydrogenation catalyst according to claim 1, characterizedin that said VIB group element is one or more selected from the groupconsisting of chromium, molybdenum and tungsten.
 7. The selectivenickel-based hydrogenation catalyst according to claim 1, characterizedin that the VIB group element oxide in the catalyst is in the amount of3-6%.
 8. A method for preparing the selective nickel-based hydrogenationcatalyst according to claim 1, comprising: adding silica or itsprecursor and alkaline earth metal oxide or its precursor into analumina carrier so as to form a first mixture; calcinating the firstmixture at the temperature of 800-1100° C. for 3-6 hours to form amodified alumina carrier; adding soluble salts of nickel, rare earthelement and VIB group element into water so as to form a solution;adjusting the pH of the solution to 4-5 following full dissolution ofthe soluble salts to form an impregnating solution; impregnating themodified alumina carrier with the impregnating solution to form a secondmixture; after impregnating, drying the second mixture at thetemperature of 40-120° C.; and after drying, calcinating the secondmixture at the temperature of 350-450° C. for 3-6 hours, therebyobtaining the resultant catalyst.
 9. The method according to claim 8,characterized in that the modified alumina carrier is prepared by:adding silica sol, nitric acid and water into alumina hydrate so as toform a third mixture; after kneading and extruding the third mixture,drying the third mixture at the temperature of 40-120° C.; after drying,calcinating the third mixture at the temperature of 300-600° C. for 4-6hours so as to form a carrier; impregnating the carrier with animpregnating solution formed by adding alkaline earth metal oxide intowater; after impregnating, drying the carrier at the temperature of40-120° C.; and after drying, calcinating the carrier at the temperatureof 800-1100° C. for 4-6 hours, thereby forming the modified aluminacarrier.